Process for preparing modified v-ti-p catalysts for synthesis of 2,3-unsaturated carboxylic acids

ABSTRACT

The invention relates to a catalyst composition comprising a mixed oxide of vanadium, titanium, and phosphorus modified with alkali metal. The titanium component is derived from a water-soluble, redox-active organo-titanium compound. The catalyst composition is highly effective at facilitating the vapor-phase condensation of formaldehyde with acetic acid to generate acrylic acid, particularly using an industrially relevant aqueous liquid feed.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a continuation application of U.S. patentapplication Ser. No. 13/234,323 filed Sep. 16, 2011.

FIELD OF THE INVENTION

The invention generally relates to the field of catalysis and, inparticular, to mixed oxide catalysts modified with at least one alkalimetal for the preparation of 2,3-unsaturated carboxylic acids.

BACKGROUND OF THE INVENTION

2,3-Unsaturated carboxylic acids and esters can be prepared from thereaction of a formaldehyde (H₂CO) source and a saturated carboxylic acidor ester containing one less carbon atom. Thus, acrylic and methacrylicacid derivatives can be prepared from the condensation of a formaldehydesource with acetic or propionic acid derivatives, respectively. Thereaction produces one equivalent of water for each equivalent ofcarboxylic acid derivative reacted.

Although a number of catalysts have been proposed for this reaction,catalysts containing acidic vanadium and phosphorus oxides are among themost efficient, especially when a third component such as titanium orsilicon is present in the catalyst. Water, however, tends to inhibit thecondensation reaction with these catalysts. The use of formalin—whichtypically contains about 37 weight percent formaldehyde in water—as astarting material, therefore, is less efficient. Methanol can also be aninhibitor for the condensation reaction, and, since formalin can alsocontain methanol, the efficiency can be further lowered. When acarboxylic acid is the reactant, the presence of methanol in formalincan create a mixture of acids and methyl esters. And when an ester isthe reactant, the water in formalin can create a mixture of acids andesters.

Industrial grade aqueous formaldehyde contains about 55 weight percentformaldehyde. It is relatively inexpensive and, therefore, is aneconomical source of this reactant. Thus, there is a need in the art forcatalysts that are capable of condensing formaldehyde with alkanoicacids or esters in the vapor phase and that are tolerant of water in thefeedstock. Ideally, such catalysts would also provide a high conversionof formaldehyde along with a high selectivity to the acrylic product.

Vanadium-titanium-phosphorus (V—Ti—P) mixed oxides are the best knowncatalysts for generating acrylic acid from the condensation offormaldehyde and acetic acid. But the preparation of these catalysts canbe dangerous and is not amenable to scale-up. Typically, the titaniumcomponent is incorporated into these catalysts by first hydrolyzingliquid titanium chloride. This step, unfortunately, generates largequantities of hydrochloric acid fumes. Thus, there is also a need in theart for methods of preparing V—Ti—P mixed oxide catalysts that are saferand more amenable to industrial production.

In addition to the use of an industrially relevant formaldehyde feedsource and the elimination of titanium chloride from the catalystpreparation, there is a need to further improve the yield offormaldehyde to the acrylic product as compared to avanadium-titanium-phosphorus (V—Ti—P) catalyst.

The present invention addresses these needs as well as others that willbe apparent from the following description and claims.

SUMMARY OF THE INVENTION

In a first aspect, the present invention provides a catalyst compositioncomprising a mixed oxide of vanadium (V), titanium (Ti), phosphorus (P),and alkali metal (M). The titanium component of the catalyst compositionis derived from a water-soluble, redox-active organo-titanium compound.

In a second aspect, the present invention provides a method forpreparing a catalyst composition comprising a mixed oxide of vanadium(V), titanium (Ti), phosphorus (P), and alkali metal (M). The methodcomprises the steps of:

(a) providing an aqueous solution comprising a water-soluble,redox-active organo-titanium compound;

(b) adding a vanadium compound, a phosphorus compound, and an alkalimetal compound to the aqueous titanium solution to form a mixture ofcatalyst components;

(c) heat-treating the mixture;

(d) removing water from the heat-treated mixture to obtain a solidresidue comprising the catalyst components; and

(e) calcining the solid residue at an elevated temperature in thepresence of air to obtain the catalyst composition.

In a third aspect, the present invention provides a process forpreparing a 2,3-unsaturated carboxylic acid. The process comprises thestep of contacting a formaldehyde source with a carboxylic acid in thepresence of a condensation catalyst under vapor-phase condensationconditions to obtain the 2,3-unsaturated carboxylic acid. Thecondensation catalyst comprises a mixed oxide of vanadium (V), titanium(Ti), phosphorus (P), and alkali metal (M). The titanium component ofthe condensation catalyst is derived from a water-soluble, redox-activeorgano-titanium compound.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a graph showing the X-ray diffraction pattern of the catalystof Example 1.

FIG. 2 is a graph showing the X-ray diffraction pattern of the catalystof Comparative Example 1.

FIG. 3 is a graph showing the X-ray diffraction pattern of the catalystof Comparative Example 2.

FIG. 4 is a graph showing the X-ray diffraction pattern of the V—Ti—Pcatalyst of Comparative Example 3.

FIG. 5 is a graph showing comparison of V—Ti—P catalyst performance.

DETAILED DESCRIPTION OF THE INVENTION

It has been surprisingly discovered that V—Ti—P-M mixed oxide catalystscan be prepared from a water-soluble, redox-active organo-titaniumsource. Employing such a titanium source can provide an inherentlysafer, and more practical and rapid route to V—Ti—P-M materials. Inaddition, it has been surprisingly discovered that the resultingcatalysts can have a higher surface area and acidity, and can be moreactive for acrylic acid formation when an aqueous formaldehyde sourceand acetic acid are used as the feed.

Thus, in a first aspect, the present invention provides a catalystcomposition comprising a mixed oxide of vanadium (V), titanium (Ti),phosphorus (P), and alkali metal (M). The titanium component of thecatalyst composition is derived from a water-soluble, redox-activeorgano-titanium compound (sometimes referred to herein as simply“water-soluble titanium compound,” “organo-titanium compound,” or“titanium compound”).

As used herein, the term “and/or,” when used in a list of two or moreitems, means that any one of the listed items can be employed by itself,or any combination of two or more of the listed items can be employed.For example, if a composition is described as containing components A,B, and/or C, the composition can contain A alone; B alone; C alone; Aand B in combination; A and C in combination; B and C in combination; orA, B, and C in combination.

It is to be understood that the mention of one or more process stepsdoes not preclude the presence of additional process steps before orafter the combined recited steps or intervening process steps betweenthose steps expressly identified. Moreover, the lettering of processsteps or ingredients is a convenient means for identifying discreteactivities or ingredients and the recited lettering can be arranged inany sequence, unless otherwise indicated.

By “water-soluble,” it is meant that the organo-titanium compound candissolve in water at 20° C. and 1 atm absolute (101.325 kPa) to form ahomogeneous solution of at least 1 weight percent of the organo-titaniumcompound. Preferably, the compound can dissolve in water to form ahomogeneous solution of at least 25 weight percent. More preferably, thecompound can dissolve in water to form a homogeneous solution of atleast 40 weight percent.

By “redox-active,” it is meant that the organic ligand of theorgano-titanium compound is capable of reducing the oxidation state ofvanadium from +5 to +4, +5 to +3, or +4 to +3. Alternatively, theorgano-titanium compound is “redox-active” if the derivative of theorgano-titanium compound, in the aqueous mixture used to make thecatalyst, is capable of reducing the oxidation state of vanadium from +5to +4, +5 to +3, or +4 to +3.

Examples of water-soluble, redox-active organo-titanium compoundsinclude titanium lactates, titanium alkanolamines, and titaniumacetylacetonates. Such compounds are commercially available, such asfrom Dorf Ketal under the tradename TYZOR®. Practical examples of suchcompounds include titanium(IV) bis(ammonium lactate)dihydroxide(TBALDH), titanium diethanolamine, titanium triethanolamine, andtitanium acetylacetonate.

Examples of alkali metal include lithium, sodium, potassium, rubidium,and cesium. In one aspect, the alkali metal comprises potassium. Inanother aspect, the alkali metal comprises potassium and thewater-soluble redox-active organo-titanium compound comprisestitanium(IV) bis(ammonium lactate)dihydroxide.

The catalyst composition according to the present invention can have thegeneral formula VTi_(a)P_(b)M_(c)O_(d), wherein a=0.3 to 6.0, preferably1.0 to 4.0; b=2.0 to 13.0, preferably 4.0 to 10.0; c=0.01 to 1.25,preferably 0.25 to 0.75; and d is the number of atoms required tosatisfy the valences of the components other than oxygen.

The catalyst composition according to the present invention can beprimarily amorphous in structure. One skilled in the art recognizes thatan amorphous catalyst composition can have a small amount of crystallinestructure caused, for example, by impurities. By “amorphous” or“primarily amorphous” it is meant that the catalyst composition containsless than 10 weight percent crystalline material. The percentcrystallinity is calculated based on the integrated intensities of anX-Ray diffraction from the individual diffraction patterns with peaks ofcrystallite size greater than 30 Å defined as crystalline and peaks ofcrystallite size less than or equal to 30 Å defined as amorphous.

The catalyst composition of the invention can be supported on an oxidesupport. Suitable oxide supports include silica, alumina, titaniumoxide, zirconium oxide, and titanium or zirconium pyrophosphates. Otheroxide supports may be used provided that they are inert to the desiredcatalytic reaction. The supports should be physically robust andpre-shaped. The term “pre-shaped” is used in this context to mean thatthe shape of the final catalyst is essentially the same as the startingsupport. The pre-shaped oxides typically can have average particlediameter sizes ranging from about 0.1 millimeter (mm) to about 20 mm.They can be in any common form such as extrudates, compressed pellets,or bulk solid that has been pulverized to the desired mesh size. Theymay also be in a variety of shapes such as rods, stars, cylinders,spheres, or broken chunks.

In accordance with a second aspect of the invention, the catalystcomposition according to the present invention can be prepared using thefollowing general steps:

(a) providing an aqueous solution comprising the water-soluble,redox-active organo-titanium compound;

(b) adding a vanadium compound, a phosphorus compound, and an alkalimetal compound to the aqueous titanium solution to form a mixture ofcatalyst components;

(c) heat-treating the mixture;

(d) removing water from the heat-treated mixture to obtain a solidresidue comprising the catalyst components; and

(e) calcining the solid residue at an elevated temperature in thepresence of air to obtain the catalyst composition.

The aqueous solution containing the water-soluble titanium compound maybe obtained directly from commercial sources or may be made bydissolving the titanium compound in water. The concentration of theaqueous titanium solution can vary over a wide range. For example, thesolution can have a titanium compound concentration in the range of 25to 75 wt %, or 30 to 70 wt %, or 50 to 60 wt %.

The mode of adding the vanadium compound, the phosphorus compound, andthe alkali metal compound to the aqueous titanium solution is notparticularly limiting. For example, the vanadium compound, thephosphorus compound, and/or the alkali metal compound may be blendedtogether to form a physical mixture or a reaction product, before beingadded to the aqueous titanium solution. Alternatively, the vanadiumcompound, phosphorus compound and/or alkali metal compound may be addedsequentially in any order or simultaneously to the aqueous titaniumsolution. Thus, as used herein, the expression “adding a vanadiumcompound, a phosphorus compound, and a alkali metal compound” can referto the addition of the vanadium compound, the phosphorus compound, andthe alkali metal compound separately and/or collectively as a physicalmixture and/or as a reaction product of any combination of thecompounds.

Similarly, the heat-treating step and the water-removing step may beconducted sequentially or simultaneously. For example, in the case ofwater removal by distillation or evaporation, the heat-treating step cantake place during the distillation or evaporation.

The heat-treating step may be conducted over a wide temperature range,such as from above ambient up to 200° C. or higher. The purpose of theheat-treating step is to facilitate mixing and/or reaction among thecatalyst precursors. Depending on the catalyst precursors and thetemperature employed, the heat-treating step may be carried out fromseveral minutes to hours or days.

The water-removal step may be accomplished in a number of ways. Forexample, as mentioned above, water may be removed by distillation orevaporation. Alternatively, as discussed in more detail below, thecatalyst components can be precipitated out of solution by adding ananti-solvent to the mixture. The water can then be removed by decantingor filtration.

Following the water-removal step, which may include a subsequent dryingstep, the resulting solid residue may be crushed and sieved to obtain adesired particle size. The sieved catalyst particles can then becalcined in one or more stages in air prior to use. The calciningtemperature is normally in the range of 200° C. to 800° C. Preferably,the calcining temperature ranges from 300° C. to 500° C. The calciningstep is typically carried out for 1 to 10 hours, and preferably for 2 to8 hours. Upon calcining, the mixed oxide catalyst according to theinvention is formed.

In addition to the water-soluble titanium compounds mentioned above, thecatalyst precursors may be ammonium salts, halides, oxyacids, oxyacidsalts, hydroxides, or oxides of vanadium, titanium, phosphorus, andalkali metal.

The vanadium compound is preferably water soluble. Examples of suchcompounds include vanadium trichloride, vanadium(IV) sulfate oxidehydrate, and ammonium vanadate optionally treated with aqueous oxalicacid and/or lactic acid. Other water-soluble vanadium sources can alsobe used.

The phosphorus compound is also preferably water soluble. The phosphoruscompound should be converted to phosphorus oxides when calcined. Suchphosphorus compounds include phosphoric acid, phosphorous acid, andammonium salts of these acids.

The alkali metal may contain lithium, sodium, potassium, rubidium,and/or cesium. The alkali metal compound is also preferably watersoluble. Examples of such compounds include potassium nitrate, potassiumnitrite, potassium sulfate, potassium carbonate, potassium phosphate,potassium metavanadate, lithium hydroxide, lithium carbonate, lithiumnitrate, lithium phosphate, lithium sulfate, lithium pyrophosphate,rubidium carbonate, rubidium hydroxide, rubidium nitrate, sodiumbisulfate, sodium bisulfite, sodium carbonate, sodium hydroxide, sodiumlactate, sodium metabisulfite, sodium metavanadate, sodium nitrate,sodium nitrite, sodium phosphate, sodium pyrophosphate, sodium sulfate,cesium carbonate, cesium hydroxide, cesium nitrate, cesiumorthovanadate, cesium sulfate, or mixtures thereof.

A reducing compound can be added to the reaction mixture to impartadditional surface area to the resulting catalyst composition. Lacticacid is preferred for this purpose, but other compounds bearingbifunctional groups such as citric acid, glycolic acid, oxalic acid,ethylene glycol, butane diol, hexane diol, or pentane diol may also beused. Use of these surface area reagents is optional, but is generallypreferred.

In one aspect of the invention the catalyst composition is prepared withthe organo-titanium compound comprising titanium(IV) bis(ammoniumlactate)dihydroxide and the alkali metal comprising potassium.

A practical example of a method for preparing the catalyst compositionaccording to the invention includes mixing a 50 wt % aqueous solution ofTBALDH with a solution of ammonium metavanadate, phosphoric acid, andpotassium nitrate in water and, optionally, lactic acid; heating themixture at 130° C. under agitation; removing water from the heat-treatedmixture by distillation; and calcining the resulting residue at 300° C.and then at 450° C. in air.

Alternatively, according to another embodiment of the invention, thecatalyst composition may be prepared as described above except that awater-miscible non-solubilizing solvent, or “anti-solvent,” is added tothe reaction/heat-treating vessel to precipitate out the majority of thecatalyst components after the heat-treating step. In this way, energyintensive water removal by distillation can be avoided, and the catalystcomposition may instead be collected by filtration followed bycalcination. The anti-solvent may be polar compounds such as alcohols,ketones, aldehydes, ethers, or esters. Alcohols such as ethanol arepreferred as the anti-solvent.

The catalyst composition according to the present invention can have thegeneral formula VTi_(a)P_(b)M_(c)O_(d), wherein a=0.3 to 6.0, preferably1.0 to 4.0; b=2.0 to 13.0, preferably 4.0 to 10.0; c=0.01 to 1.25,preferably 0.25 to 0.75; and d is the number of atoms required tosatisfy the valences of the components other than oxygen.

The catalyst composition of the invention can be supported on an oxidesupport. Suitable oxide supports include silica, alumina, titaniumoxide, zirconium oxide, and titanium or zirconium pyrophosphates. Otheroxide supports may be used provided that they are inert to the desiredcatalytic reaction. The supports should be physically robust andpre-shaped. The term “pre-shaped” is used in this context to mean thatthe shape of the final catalyst is essentially the same as the startingsupport. The pre-shaped oxides typically can have average particlediameter sizes ranging from about 0.1 millimeter (mm) to about 20 mm.They can be in any common form such as extrudates, compressed pellets,or bulk solid that has been pulverized to the desired mesh size. Theymay also be in a variety of shapes such as rods, stars, cylinders,spheres, or broken chunks. Many of these oxide supports are availablecommercially, and their use simplifies the preparation of the catalystcomposition of the invention, although this is not a requirement of theinvention. The pre-shaped support can be added to the mixture ofcatalyst components before the heat-treating step (c).

In supported embodiments, the titanium, the vanadium, and the alkalimetal components can be loaded onto the support separately or together.A preferred technique is to dissolve the desired amount of ammoniumvanadate, potassium nitrate, and oxalic acid or lactic acid in theaqueous TBALDH solution. This solution can be diluted if desired andthen used to impregnate the oxide support using the incipient wetnesstechnique. The impregnated support is then dried at about 110° C. Thedried support containing the vanadium, titanium, and alkali metal isthen impregnated with the desired amount of the aqueous solution of thephosphorus compound.

The order of impregnation normally is not critical. Co-impregnation ofthe support with vanadium, titanium, and alkali metal followed byimpregnation with phosphorus after drying can be used as illustratedabove.

Incipient wetness techniques can be used for all of the impregnations.If a higher loading is required, more solution than required forincipient wetness can be used followed by evaporation of the solvent. Ifdesired, the solutions can be applied to the outer regions of the oxidesupport.

After the vanadium, titanium, phosphorus, and alkali metal componentshave been applied to the support, the catalyst can be calcined, forexample, at about 450° C.

A reducing compound can be added to the reaction mixture to impartadditional surface area to the resulting catalyst composition. Lacticacid is preferred for this purpose, but other compounds bearingbifunctional groups (i.e., bifunctional compounds) such as citric acid,glycolic acid, oxalic acid, ethylene glycol, butane diol, hexane diol,or pentane diol may also be used. Use of these surface area reagents isoptional, but is generally preferred. In one aspect of the invention,the bifunctional compound can be added to the mixture of catalystcomponents before the heat-treating step (c). In one aspect of theinvention, the bifunctional compound can comprise lactic acid.

The quaternary V—Ti—P-M catalyst composition disclosed herein isprimarily amorphous, as determined by x-ray diffraction analysis.Interestingly, the invention V—Ti—P-M catalyst composition prepared withTBALDH, for example, produces acrylic acid in significantly higher yield(>15%) than unmodified V—Ti—P material prepared with TBALDH, andproduces acrylic acid in significantly higher yield (>30%) thanunmodified V—Ti—P material prepared with titanium chloride when a 55weight percent aqueous formaldehyde feed is used. This result occurseven though all three catalysts are primarily amorphous materials.

The propensity for a water-soluble titanium compound, such as TBALDH, toform an active V—Ti—P-M catalyst comes as a surprise, since titaniumsources other than TiCl₄ have been shown to produce inferior catalystsfor acrylic acid production. See, for example, M. Ai, Applied Catalysis,Vol. 48, pp. 51-61 (1989). For example, when titanium dioxide isemployed as a titanium precursor, the resulting material fails togenerate acrylic acid from formaldehyde and acetic acid. It has beenreported elsewhere that TiO₂ can form catalytically active materials foracrylate production (M. Abon et al., J. Catalysis, Vol. 156, pp. 28-36(1995)); however, this result could not be reproduced.

Also unexpected is the fact that exogenous lactic acid is no longerrequired in the catalyst synthesis, for example, when TBALDH is used.When lactic acid is omitted from the catalyst preparation involvingtetrachlorotitanium, the resulting material is highly crystalline, asdetermined by x-ray diffraction, but is relatively inactive towardacrylic acid synthesis. However, V—Ti—P-M materials prepared withTBALDH, for example, in the absence of lactic acid are amorphous and areconsiderably more active and selective. Avoiding lactic acid addition isappealing, since it minimizes the amount of steps in the catalystsynthesis and results in less organic material that must be combustedduring air calcination.

One skilled in the art recognizes that the possession of a markedlyacidic property is necessary for a catalyst to promote the condensationof formaldehyde and alkonoic acids or esters, and that a certain extentof basic property is also required. However, the ideal concentration ofeach property (i.e., number of acid sites and number of basic sites) isnot known. There exist several techniques for determining the relativeacidity and basicity of a heterogeneous catalyst, but it is hard to makecomparisons across different techniques. One technique for measuring theconcentration of acidic and basic sites on a solid surface is to performtemperature programmed desorption (TPD) experiments. For example,iso-propanol adsorption to a known quantity of catalyst sample followedby heating will form propylene if the material has acidic sites andacetone if basic sites are present. Multiple acidic or basic sites maybe present in the sample, each with a distinct acid or base strength andeach present in varying concentration. The amount of moles of eachproduct (propylene or acetone) per gram of sample is a measure of thetotal concentration of each type of reactive site (acid or base).Therefore, the number of different acid or base sites may be inferredfrom the desorption curve in the TPD profile of each sample. Propylene,for example, will desorb from the varying acidic sites at differenttemperatures if more than one type of acid site is present in thesample. The magnitude of the maximum temperature (Tmax) of eachpropylene desorption curve is an indication of the corresponding acidsite strength. In this case, higher temperature implies stronger acidicsites, or in other words, the reactant is bound more tightly to thesurface at this site and requires more energy to initiate reaction anddesorption of the product. Propylamine TPD experiments are also usefulfor acidity measurements. Desorption of physisorbed propylamine is areflection of Lewis type acidity while desorption of propylene, whicharises from propylamine chemisorption, is a measure of Brønsted acidity.

Alkali metal oxides typically possess basic characteristics and V—Ti—Poxides are predominantly acidic solids. Thus, it would be reasonable toexpect that potassium inclusion in the V—Ti—P material would neutralizea portion of the acid sites on the catalyst surface. Indeed, the V—Ti—Pcatalyst possessing 2.5 wt. % potassium is considerably more basic,however it is also unexpectedly more acidic than the unmodifiedmaterial. The formaldehyde conversion over the 2.5 wt. % potassium is,on average, more than 25% higher (i.e., percentage points higher, thesimple difference in conversions) than that of the unmodified catalystmade with the same process; the acrylic acid yield is higher by about15%. The formaldehyde conversion over the 2.5 wt. % potassium is, onaverage, more than 45% higher than that of the unmodified catalyst madeby the process described in M. Ai, Applied Catalysis, Vol. 48, pp. 51-61(1989) and JP 1989-068335A; the acrylic acid yield is higher by over33%. This beneficial potassium effect comes as a surprise since higherpotassium loadings do not necessarily produce more active V—Ti—Pcatalysts. Increasing the potassium concentration to 9.25 wt. % forexample, affords a catalyst that converts formaldehyde in less than 25%and gives an acrylate yield of less than 20%.

Without being bound by any theory, applicants note that comparison ofacid and base properties may not be sufficient to fully rationalize theimproved performance of the 2.5 wt. % potassium catalyst since thiscatalyst has a higher than expected acid site content relative to theunmodified catalyst. The factors controlling the higher formaldehydeconversion could instead arise from defects in the catalyst imparted bythe potassium promoter or from changes in the average vanadium oxidationstate of the material.

In a third aspect, the present invention provides a process forpreparing a 2,3-unsaturated carboxylic acid, such as acrylic acid ormethacrylic acid. Reference to “carboxylic acid” in this contextincludes the corresponding carboxylic acid ester, such as acrylate andmethacrylate.

The process of the invention comprises the step of contacting aformaldehyde source with a carboxylic acid in the presence of acondensation catalyst under vapor-phase condensation conditions toobtain the 2,3-unsaturated carboxylic acid. The condensation catalystcomprises a mixed oxide of vanadium (V), titanium (Ti), phosphorus (P),and alkali metal (M). The titanium component of the condensationcatalyst is derived from a water-soluble, redox-active organo-titaniumcompound, as described herein.

The 2,3-unsaturated carboxylic acid can be prepared with good yield,conversion, and selectivity. By “yield” it is meant the (moles ofproduct)/(moles of reactant fed)*100. For example, the % yield ofacrylic acid from formaldehyde is the (moles of acrylic acid)/(moles offormaldehyde fed)*100. By “conversion” it is meant the (moles ofreactant fed—moles of unreacted reactant)/(moles of reactant fed)*100.For example, the formaldehyde conversion is (moles of formaldehydefed—moles of unreacted formaldehyde)/(moles of formaldehyde fed)*100. By“selectivity” it is meant (moles of product)/(moles of reactantfed—moles of unreacted reactant)*100. For example, % selectivity toacrylic acid from formaldehyde is (moles of acrylic acid)/(moles offormaldehyde fed—moles of unreacted formaldehyde)*100. One skilled inthe art recognizes that yield is also equal to conversion timesselectivity. When comparing examples, such as, Example B has an 80%formaldehyde conversion and Example C has a 60% formaldehyde conversion,the formaldehyde conversion of Example B is said to be 20% higher thanExample C. In other words, comparisons are simply the mathematicaldifference in the percentages from one example to another.

The formaldehyde source for use in the present invention is notparticularly limiting. It can be anhydrous formaldehyde itself,1,3,5-trioxane (sometimes referred to herein as simply “trioxane”),dimethoxymethane, or diacetoxymethane. Alternatively, the formaldehydesource may be an aqueous solution of formaldehyde. The aqueousformaldehyde solution can contain, for example, from 30 to 65 weightpercent formaldehyde. Examples of such solutions include formalin (37 wt% formaldehyde) and industrial grade aqueous formaldehyde (55 wt %formaldehyde). The aqueous formaldehyde solution may be obtainedcommercially, by oxidation of methanol, or by blending water withtrioxane, for example, in a molar ratio of approximately 4:1.

The carboxylic acid should have at least 2 hydrogen atoms in theposition alpha to the carboxylic acid group. The carboxylic acid ispreferably an aliphatic carboxylic acid having 2 to 4 carbon atoms.Acetic and propionic acids are preferred carboxylic acids. The mostpreferred carboxylic acid is acetic acid. The term “carboxylic acid” inthis context includes the corresponding carboxylic acid ester, whenformation of the 2,3-unsaturated carboxylic acid ester is desired.Examples of such carboxylic acid esters include acetate and propionate.

The description of the catalyst composition and the process for makingthe catalyst composition herein above, such as, for example, thedescription of vanadium, titanium, phosphorus, and alkali metalcompounds, the catalyst formula, the alkali metals, the pre-shapedsupports, the water removal step, and the bifunctional compound, applyto the process for preparing a 2,3-unsaturated carboxylic acid.

The molar ratio of the formaldehyde component to the carboxylic acidcomponent may be from 0.1 to 10, preferably from 0.2 to 5, and morepreferably from 0.2 to 2. The molar ratio of water to the formaldehydecomponent may be from 0 to 5, preferably from 0 to 3, and morepreferably from 0 to 1.5.

The process can be operated at a temperature from 200° C. to 400° C.,preferably from 225° C. to 375° C., and more preferably from 275° C. to375° C.

The process can be run at a pressure from 0.1 to 10 bars absolute(bara), preferably from 0.5 to 5 bara, and more preferably from 1 to 1.5bara.

In certain embodiments of the process of the invention, the liquid feedrate can range from 1.0 to 1000 mL/kg catalyst/minute, and preferablyfrom 10 to 100 mL/kg catalyst/minute.

In other embodiments of the process of the invention, the reactants canbe fed to the condensation reactor with oxygen along with an inertcarrier gas such as nitrogen or oxygen-depleted air. Gases recycled fromthe process can be used. The inert gas component can be present atconcentrations ranging from 0 to 90 mole % of the total feed, preferablyfrom 25 to 85 mole %, and more preferably from 30 to 80 mole %. Theconcentration of the oxygen component can range from 0.5 to 6 mole %,preferably from 2 to 5 mole %, and more preferably from 3 to 4 mole %.Low levels of oxygen allow for coke to build up on the catalyst. On theother hand, high levels of oxygen can lead to excessive combustion ofreactants and products.

Inhibitors such as hydroquinone may be added to the 2,3-unsaturatedcarboxylic acid product to minimize polymerization.

LISTING OF NON-LIMITING EMBODIMENTS

Embodiment A is a catalyst composition comprising a mixed oxide ofvanadium (V), titanium (Ti), phosphorus (P), and alkali metal (M)wherein the titanium component is derived from a water-soluble,redox-active organo-titanium compound.

The catalyst composition of Embodiment A which has the general formulaVTi_(a)P_(b)M_(c)O_(d), wherein a is a number from 0.3 to 6.0, b is anumber from 2.0 to 13.0, c is a number from 0.01 to 1.25, and d is thenumber of atoms required to satisfy the valences of V, Ti, P, and M; orwherein a ranges from 1.0 to 4.0, b ranges from 4.0 to 10.0, and cranges from 0.25 to 0.75.

The catalyst composition of Embodiment A or Embodiment A with one ormore of the intervening features wherein the alkali metal is selectedfrom at least one of lithium, sodium, potassium, rubidium, and cesium.

The catalyst composition of Embodiment A or Embodiment A with one ormore of the intervening features wherein the organo-titanium compoundcomprises titanium(IV) bis(ammonium lactate)dihydroxide and the alkalimetal comprises potassium.

The catalyst composition of Embodiment A or Embodiment A with one ormore of the intervening features which further comprises a pre-shapedsupport.

The catalyst composition of Embodiment A or Embodiment A with one ormore of the intervening features which further comprises a pre-shapedsupport, wherein the pre-shaped support comprises silica, alumina,titanium oxide, titanium pyrophosphate, zirconium oxide, or zirconiumpyrophosphate.

The catalyst composition of Embodiment A or Embodiment A with one ormore of the intervening features which further comprises a pre-shapedsupport, wherein the pre-shaped support has a particle size ranging from0.1 mm to 20 mm.

Embodiment B is a method for preparing a catalyst composition comprisinga mixed oxide of vanadium (V), titanium (Ti), phosphorus (P), and alkalimetal (M). The method comprises the steps of:

-   -   a. providing an aqueous solution comprising a water-soluble,        redox-active organo-titanium compound;    -   b. adding a vanadium compound, a phosphorus compound, and an        alkali metal compound to the aqueous titanium solution to form a        mixture of catalyst components;    -   c. heat-treating the mixture;    -   d. removing water from the heat-treated mixture to obtain a        solid residue comprising the catalyst components; and    -   e. calcining the solid residue at an elevated temperature in the        presence of air to obtain the catalyst composition.

The method of Embodiment B wherein the water removing step (d) comprisesdistillation or evaporation.

The method of Embodiment B wherein the water removing step (d) comprisesadding an anti-solvent to the mixture to precipitate out the catalystcomponents and separating the precipitate from the liquid to obtain thesolid residue.

The method of Embodiment B wherein the water removing step (d) comprisesadding an anti-solvent to the mixture to precipitate out the catalystcomponents and separating the precipitate from the liquid to obtain thesolid residue, and wherein the precipitate is separated from the liquidby filtration.

The method of Embodiment B wherein the water removing step (d) comprisesadding an anti-solvent to the mixture to precipitate out the catalystcomponents and separating the precipitate from the liquid to obtain thesolid residue, wherein the precipitate is separated from the liquid byfiltration, and wherein the anti-solvent is a polar compound selectedfrom alcohols, ketones, aldehydes, ethers, and esters; or wherein theanti-solvent is an alcohol.

The method of Embodiment B or Embodiment B with one or more of theintervening features wherein the catalyst composition has the generalformula VTi_(a)P_(b)M_(c)O_(d), wherein a is a number from 0.3 to 6.0, bis a number from 2.0 to 13.0, c is a number from 0.01 to 1.25, and d isthe number of atoms required to satisfy the valences of V, Ti, P, and M;or wherein a ranges from 1.0 to 4.0, b ranges from 4.0 to 10.0, and cranges from 0.25 to 0.75.

The method of Embodiment B or Embodiment B with one or more of theintervening features wherein the organo-titanium compound comprisestitanium(IV) bis(ammonium lactate)dihydroxide and the alkali metalcomprises potassium.

The method of Embodiment B or Embodiment B with one or more of theintervening features wherein the catalyst composition further comprisesa pre-shaped support.

The method of Embodiment B or Embodiment B with one or more of theintervening features which further comprises a pre-shaped support,wherein the pre-shaped support comprises silica, alumina, titaniumoxide, titanium pyrophosphate, zirconium oxide, or zirconiumpyrophosphate.

The method of Embodiment B or Embodiment B with one or more of theintervening features which further comprises a pre-shaped support,wherein the pre-shaped support has a particle size ranging from 0.1 mmto 20 mm.

The method of Embodiment B or Embodiment B with one or more of theintervening features wherein the catalyst composition further comprisesa pre-shaped support, and wherein the pre-shaped support is added to themixture of catalyst components before the heat-treating step (c).

The method of Embodiment B or Embodiment B with one or more of theintervening features which further comprises adding a bifunctionalcompound to the mixture of catalyst components before the heat-treatingstep (c), wherein the bifunctional compound comprises citric acid,lactic acid, glycolic acid, oxalic acid, ethylene glycol, butane diol,pentane diol, or hexane diol; or wherein the bifunctional compoundcomprises lactic acid.

Embodiment C is a process for preparing a 2,3-unsaturated carboxylicacid. The process comprises the step of contacting a formaldehyde sourcewith a carboxylic acid in the presence of a condensation catalyst undervapor-phase condensation conditions to obtain the 2,3-unsaturatedcarboxylic acid. The condensation catalyst comprises a mixed oxide ofvanadium (V), titanium (Ti), phosphorus (P), and alkali metal (M). Thetitanium component of the condensation catalyst is derived from awater-soluble, redox-active organo-titanium compound.

The process of Embodiment C wherein the formaldehyde source comprisesformaldehyde, 1,3,5-trioxane, dimethoxymethane, or diacetoxymethane andthe carboxylic acid comprises acetic acid or propionic acid.

The process of Embodiment C or Embodiment C with one or more of theintervening features wherein the formaldehyde source comprises anaqueous solution of formaldehyde, 1,3,5-trioxane, dimethoxymethane, ordiacetoxymethane and the carboxylic acid comprises acetic acid orpropionic acid.

The process of Embodiment C or Embodiment C with one or more of theintervening features wherein the formaldehyde source comprises anaqueous solution of formaldehyde, 1,3,5-trioxane, dimethoxymethane, ordiacetoxymethane and the carboxylic acid comprises acetic acid orpropionic acid, and wherein the aqueous solution comprises from 30 to 65weight percent formaldehyde.

The process of Embodiment C or Embodiment C with one or more of theintervening features wherein the alkali metal is selected from at leastone of lithium, sodium, potassium, rubidium, and cesium.

The process of Embodiment C or Embodiment C with one or more of theintervening features wherein the organo-titanium compound comprisestitanium(IV) bis(ammonium lactate)dihydroxide and the alkali metalcomprises potassium.

The process of Embodiment C or Embodiment C with one or more of theintervening features wherein the catalyst composition further comprisesa pre-shaped support.

The process of Embodiment C or Embodiment C with one or more of theintervening features which further comprises a pre-shaped support,wherein the pre-shaped support comprises silica, alumina, titaniumoxide, titanium pyrophosphate, zirconium oxide, or zirconiumpyrophosphate.

The process of Embodiment C or Embodiment C with one or more of theintervening features which further comprises a pre-shaped support,wherein the pre-shaped support has a particle size ranging from 0.1 mmto 20 mm.

This invention can be further illustrated by the following workingexamples, although it will be understood that these examples areincluded merely for purposes of illustration and are not intended tolimit the scope of the invention. Unless otherwise indicated or thecontext indicates otherwise, all percentages are by weight.

Examples Materials

D/L-Lactic acid (90 wt %), ammonium metavanadate (99+ wt % NH₄VO₃),phosphoric acid (85 wt % H₃PO₄), titanium(IV) bis(ammoniumlactate)dihydroxide (50 wt. % solution in water), tetrachlorotitanium(99 wt % TiCl₄), and potassium nitrate (KNO₃) were purchased fromcommercial suppliers and used as received.

ABBREVIATIONS

XRD=Powder X-ray Diffraction, XRF=X-ray Fluorescence Spectroscopy,TPD=Temperature Programmed Desorption, SCCM=standard cubic centimetersper minute; MeOAc=methyl acetate, MeOH=methanol, MA=methyl acrylate,H2CO=formaldehyde; HOAc=acetic acid, HOPr=propionic acid,mmol=millimoles, prod=product, AA=acrylic acid,BSTFA=N,O-bis(trimethylsilyl)trifluoroacetamide, andTMSCl=trimethylsilyl chloride.

XRD Measurements

All XRD measurements were performed on a Rigaku Miniflex X-RayDiffraction Spectrometer using a Copper anode X-Ray tube operated at 30kV and 15 mA. Diffraction patterns were collected from 2.5 degree twotheta angle to 80 degree two theta angle with a sampling width of 0.02degrees and a scan speed of 1.00 degrees/min.

Crystallite size was calculated based on the measurement of the fullwidth half maximum for peaks in the diffraction pattern and use of theScherrer equation (P. N. Scherrer, Ges. Wiss. Gottingen, Math.—Phys. KI.2, 96-100, 1918). Quantitative phase analysis was calculated using arefinement algorithm base on the Rietveld method (H. M. Rietveld, J.Applied Crystallography 21, 86-91 (1988)). Percent crystallinity wascalculated based on integrated intensities from the individualdiffraction patterns with peaks of crystallite size greater than 30 Ådefined as crystalline and peaks of crystallite size less than or equalto 30 Å defined as amorphous (N. S. Murthy et al., Polymers 31, 996-1002(1990)).

TPD Measurements

TPD determinations were conducted using a Mass Spectrometer attached tothe outlet of a Micrometrics Autochem II 2920 analyzer. Thedetermination of total acidity and total basicity using isopropanol asthe probe molecule is performed as follows. Approximately 0.05 grams ofsample is weighed into a quartz U tube which is placed in a ceramicfurnace. The sample is subjected to a programmed temperature cycle thatconsists of a heat cycle to 450° C. under 10% oxygen in helium, acooling step to 40° C. Isopropanol is dosed on the sample using thevapor generator of the Micromeritics Autochem 2920 Analyzer. The vaporgenerator operates by bubbling helium through a flask containingisopropanol at room temperature. The resulting “vapor-saturated” heliumis transferred through a heated sample loop and injected over thesample. After saturating the surface of the sample, dry helium is passedover the sample to remove any physisorbed vapor. Then a final heating to˜450° C. at 20° C./min in a flowing stream of He at which time massspectral data is collected from the gas flowing through the sample. Thedetermination of Brønsted and Lewis acidity using ispropyl amine as theprobe molecule is as follows. Approximately 0.05 grams of sample isweighed into a quartz U tube which is placed in a ceramic furnace. Acontrolled gas flow is sent through the tube. The sample is subjected toa programmed temperature cycle that consists of a heat cycle to 350° C.under He and a cooling step to 40° C. Isopropyl amine is dosed on thesample using the vapor generator of the Micromeritics Autochem 2920Analyzer. The vapor generator operates by bubbling helium through aflask containing isopropyl amine at room temperature. The resulting“vapor-saturated” helium is transferred through a heated sample loop andinjected over the sample. After saturating the surface of the sample,dry helium is passed over the sample to remove any physisorbed vapor.Then a final heating to ˜500° C. at 20° C./min in a flowing stream of Heat which time mass spectral data is collected from the gas flowingthrough the sample.

Gas Chromatography Measurements

Liquid product samples were collected over a measured time period,weighed, and analyzed by gas chromatography. Samples were weighed into agas chromatography (GC) vial to a recorded weight of 0.1XXX (where X isthe actual number shown on the balance). Then, a LEAP unit was used torobotically add 200 μL of internal standard (0.7325 g dodecane in 100 mLpyridine), followed by 1.0 mL of BSTFA (w/TMSCl). The vials were thenplaced on a heat plate at 80° C. for 30 minutes. To separate allcomponents, each sample was injected on two columns running in parallelon one instrument, a Shimadzu 2010 gas chromatograph with an AOC-20autosampler. Gas Chromatography measurements were used to quantify allcomponents in the liquid product except formaldehyde.

Liquid Chromatography Measurements.

Quantitation of formaldehyde in the liquid product was performed usinghigh performance liquid chromatography after liquid product samples weresubjected to acid hydrolysis in aqueous 25% v/v H₂SO₄ at 80° C. for 30minutes. The acid hydrolysate was reacted with dinitrophenylhydrazinethen analyzed using a Phenomenex Luna C8 column using a 1:1water:acetonitrile mobile phase under isocratic conditions. Separationand detection of the 2,4-dinitrophenylhydrazone derivative offormaldehyde was carried out using an Agilent 1100 HPLC system with aUV-Vis Detector monitoring at 360 nm. The formaldehyde concentration inthe liquid product was calculated based on calibration using externalstandards prepared from formalin. The amount of formaldehyde fed to thereactor was calculated based upon the ratio of water to trioxane and theliquid feed flow rate.

Example 1 Preparation of an Amorphous V—Ti—P Catalyst with 2.5 wt %Potassium Loading and Reactor Screening with an Aqueous Liquid Feed 1.Preparation of 2.5 wt % K modified V—Ti—P Catalyst

The catalyst in this example was first prepared by suspending ammoniummetavanadate (19.54 g) and potassium nitrate (7.22 g) in 218.38 g of a50 wt % titanium(IV) bis(ammonium lactate)dihydroxide solution followedby addition of 200 mL of deionized water in a 1-L three-neck kettlereactor equipped with a distillation head and a mechanical stirrer. Thebeige suspension was stirred at 700 rpm for 10 min at room temperature,then 105.11 g of 85% phosphoric acid was added followed by a rinse withabout 50 mL of water. There was an immediate color change to brightyellow and thickening of the mixture, then a change to green then palegreen over 20 min. The stirred suspension was then heated to reflux (oilbath set at 130° C.) and about 175 mL of water was collected viadistillation over five hours, leaving a pale green semi-solid with brownflecks. After cooling to room temperature, the resulting pale greensemi-solid was scraped into a ceramic dish and calcined at 300° C. for16 h in a muffle furnace in air to give black-green solids, which weresieved through an 8×14 mesh. The 8×14 meshed pellets were then calcinedat 450° C. in a quartz tube furnace for 6 h with a 60 SCCM air flow togive pale green pellets. XRD analysis (FIG. 1) of this material revealsthat it is 100% amorphous. The surface properties and bulk compositionof the catalyst prepared in this example are summarized in Tables 1 and2.

2. Preparation of Acrylic Acid

The vapor-phase condensation experiment with molar ratio 12 aceticacid/1 trioxane/4.09 water feed was performed at 325° C., 0.093 mLliquid feed/minute, and 49 SCCM N₂ and 21 SCCM air for twenty sevenhours. The performance of the catalyst is summarized in Table 3. InTable 3, the term “Product, g” refers to the mass of the liquid productsrecovered. The term “Reactants fed, g” includes only those reactants fedas liquids to the reactor: trioxane, acetic acid, and water.

The condensation reaction of acetic acid, trioxane (the formaldehydesource), and water was performed in a 25-mm outer diameter (21 mm innerdiameter) quartz reactor tube with length=79 cm (31 inches). Heat to thereactor was provided by an Applied Test Systems series 3210 threeelement electric furnace having a heated zone 50 cm (19.5 inches) inlength. Liquid products were collected in a three-necked flask with aglycol chilled (0° C.) jacket. The three-necked flask was fitted to awater-cooled condenser, which was attached to a dry-ice condenser with atrap. The base of the receiver flask was fitted with a stopcock to allowfor draining of the liquid products.

The quartz reactor had indentations 13 cm (5 inches) up from the base ofthe tube. The region of the reactor with the indentations was situatednear the base of the heated section of the furnace. The reactor was alsofitted with a thermowell that extended from the top of the reactor toabout an inch below the indentations. The reactor was first loaded withquartz chips to about 8 inches in height above the indentations to allowthe catalyst to be positioned in the middle of the three elementfurnace. The reactor was then loaded with a 5.0 g charge of catalyst.The thermocouple in the thermowell was placed near the center of thecatalyst bed, approximately 1.5 inches up from the base of the catalystbed. Sufficient quartz chips (about 2.5 inches) were added to the regionabove the catalyst charge to reach the top of the heated region of thefurnace.

This example demonstrates that the catalyst containing 2.5 wt. %potassium produces acrylic acid from acetic acid and a 55 wt. % solutionof formaldehyde in water. The average conversion, selectivity and yieldfrom the twenty seven hour reaction are 80.5%, 86.5% and 69.5%,respectively. When compared to the performance of the unmodified V—Ti—Pcatalyst described in Comparative Example 1, the conversion and yieldusing the 2.5 wt % potassium catalyst are 25% higher and almost 15%higher, respectively. When compared to the performance of the unmodifiedV—Ti—P catalyst described in Comparative Example 3, the improvement inconversion and yield using the 2.5 wt % potassium catalyst are over 45%higher and over 30% higher, respectively.

Comparative Example 1 Preparation of an Amorphous V—Ti—P Catalyst andReactor Screening with an Aqueous Liquid Feed 1. Preparation of V(IV)H₃PO₄ Solution

The orange-beige ammonium metavanadate (19.53 g) was suspended in 50 mLof lactic acid and 200 mL of deionized water in a 500-mL single-neckedround-bottomed flask. After heating at 70° C. for 1 hour, 85%orthophosphoric acid (105.2 g) was added to the clear blue vanadiumsolution at 70° C. over a 15-minute period to give a blue-greensolution. Residual reactants were washed into the reaction flask with aminimal amount of water.

2. Preparation of V—Ti—P Catalyst

The 50 wt % titanium(IV) bis(ammonium lactate)dihydroxide solution(218.32 g) was added to a 1-L three-necked kettle reactor equipped witha condenser and a mechanical stirrer. The V/P solution from step 1 abovewas slowly poured into the Ti solution to give a blue suspension. TheV/P flask was rinsed with 30 mL of water and the contents were added tothe reaction flask. The mixture was then stirred at 700 rpm at 130° C.for 16 hours to give a blue to blue-green suspension. The water was thenremoved via distillation over 4 to 6 h (oil bath set at 130° C.), andthe resulting damp pale green solid was transferred to a ceramic dishand heated in air at 300° C. for 16 hours in a muffle furnace. Theresulting solid was then crushed and sieved through an 8×14 mesh. The8×14 meshed material was then calcined for 6 hours at 450° C. in air (60SCCM) in a quartz tube to give pale green irregularly shaped pellets.XRD analysis (FIG. 2) of this material indicated two small crystallinephases and an amorphous phase. The crystalline phases (hydrogenoxovanadium phosphate(V) hydrate and vanadium phosphorus oxide) were notcompletely resolved but were calculated to account for approximately 3%of the area of the diffraction pattern or corresponding to approximately3% crystallinity in the sample; the catalyst is primarily amorphous. Thesurface properties and bulk composition of the catalyst prepared in thisexample are summarized in Tables 1 and 2.

3. Preparation of Acrylic Acid

The vapor-phase condensation experiment was conducted in the same manneras Example 1. The performance of the catalyst is summarized in Table 4.

The average conversion, selectivity and yield from the twenty seven hourreaction are 54.8%, 99.9% and 54.6%, respectively. This exampledemonstrates that the unmodified V—Ti—P catalyst prepared using themethod of Example 1 has higher conversion and yield than the prior artcatalyst of Comparative Example 3, but has lower conversion and yieldthan the potassium modified catalyst of Example 1.

Comparative Example 2 Preparation of a 9.5 wt % K modified V—Ti—PCatalyst and Reactor Screening with an Aqueous Liquid Feed 1.Preparation of 9.5 wt % K Modified V—Ti—P Catalyst

The catalyst in this example was prepared according to the proceduredescribed in Example 1 except that 30.0 g of potassium nitrate was usedduring the initial mixing. XRD analysis (FIG. 3) of this materialreveals that it is 100% amorphous. The surface properties and bulkcomposition of the catalyst prepared in this example are summarized inTables 1 and 2.

2. Preparation of Acrylic Acid

The vapor-phase condensation experiment was carried out as described inExample 1. The performance of the catalyst is summarized in Table 5.

The average conversion, selectivity and yield from the twenty seven hourreaction are 18.2%, 101.4% and 18.1%, respectively. This exampledemonstrates that increasing the potassium concentration to 9.25%produces a modified V—Ti—P catalyst that is not as active as the 2.5 wt.% potassium catalyst of Example 1 nor as active as the unmodifiedcatalyst of Comparative Examples 1 and 3.

Comparative Example 3 Preparation of Amorphous V—Ti—P Catalyst andReactor Screening with an Aqueous Liquid Feed

The catalyst in this example was prepared according to the methodsdescribed in M. Ai, Applied Catalysis, Vol. 48, pp. 51-61 (1989) and JP1989-068335 A.

1. Ti(OH)₄ Gel Preparation

A 5-L three-necked round bottomed flask was charged with 300 mL of waterice and 300 mL of deionized water. The flask was fitted with a 125-mLaddition funnel and vented to an aqueous saturated sodium bicarbonatesolution. Tetrachlorotitanium (69.8 g) was then added slowly to thevigorously stirred water/ice mix. The reactor atmosphere was flushedinto the scrubber solution with an air flow to remove gaseous HCl. ThepH of the resulting colorless solution was between 0 and 1.

Once the solution warmed to room temperature, it was diluted with 2.5 Lof deionized water and the pH was adjusted to between 10 and 11 by theaddition of 500 mL of 5.0 M ammonium hydroxide. A bright white solidformed immediately. This material was filtered and washed with 2×1 L ofwater to give white pieces of a paste-like substance, which was airdried for up to five hours to give a white material with a gel-likeconsistency.

2. Preparation of V(IV) H₃PO₄ Solution

A V/P solution was prepared following the procedure of ComparativeExample 1, step 1.

3. Preparation of V—Ti—P Catalyst

The hydroxide gel from step 1 above was suspended in 200 mL of water ina 1-L three-necked kettle reactor equipped with a condenser andmechanically stirred at 700 to 800 rpm long enough to obtain ahomogeneous white suspension. The V/P solution from step 2 above wasslowly poured into the gel suspension to give a blue suspension. The V/Pflask was rinsed with 50 mL of water and the contents were added to thereaction flask. The mixture was then stirred at 700 to 800 rpm at 130°C. for 16 hours to give a blue to blue-green suspension.

The water was then removed via distillation over 6 h (oil bath set at130° C.) and the resulting damp pale green solid was transferred to aceramic dish and heated in air at 300° C. for 16 hours in a mufflefurnace. The resulting solid was then crushed and sieved through an 8×14mesh. The 8×14 meshed material was then calcined for 6 hours at 450° C.in air (60 SCCM) in a quartz tube to give pale green irregularly shapedpellets. The surface properties and bulk composition of the catalystprepared in this example are summarized in Tables 1 and 2. Powder x-raydiffraction analysis of the catalyst reveals that it is primarilyamorphous (FIG. 4).

4. Preparation of Acrylic Acid

The vapor-phase condensation was performed as described in Example 1.The performance of the catalyst is summarized in Table 6.

The average conversion, selectivity and yield from the twenty seven hourreaction are 34.0%, 106.3% and 36.1%, respectively. This exampledemonstrates that the V—Ti—P catalyst prepared according to the priorart did not afford acrylic acid in as high a yield as the inventioncatalyst of Example 1 when an aqueous liquid feed was used. Even thoughthe selectivity toward acrylic acid was similarly high and the reactionlifetime was comparable, the formaldehyde conversion was consistentlylower than observed in Example 1 by more than 45%.

TABLE 1 Catalyst Characterization Data Mole Ratio Potassium BET SurfaceBulk Composition Example Loading Area (m²/g) (via XRF Measurement) Ex. 1 2.5 wt. % 65 1.00V:1.96Ti:5.14P:0.39K Comp.   0 wt. % 551.00V:1.92Ti:5.34P:0.00K Ex. 1 Comp. 9.25 wt. % 441.00V:1.92Ti:5.1P:1.39K Ex. 2 Comp.   0 wt. % 201.00V:1.81Ti:5.23P:0.00K Ex. 3

TABLE 2 Catalyst Characterization Data iso-Propanol TPD n-PropylamineTPD Total Total Lewis Brønsted Acid Sites Base Sites Acid Sites AcidSites Potassium (T_(max) (T_(max) (T_(max) (T_(max) Example Loadingdesportion) desportion) desportion) desportion) Ex. 1  2.5 wt. % 80.17.3  4.8 34.4 μmol/g μmol/g μmol/g μmol/g      (128° C.) (107° C.)   (136° C.) (316,338° C.) Comp.   0 wt. % 70.6 2.8 13.6 26.6 Ex. 1μmol/g μmol/g μmol/g μmol/g      (125° C.)  (93° C.)    (115° C.)   (294° C.) Comp. 9.25 wt. % 28.4 5.9  5.0 19.7 Ex. 2 μmol/g μmol/gμmol/g μmol/g (102,187,277° C.) (107° C.) (138,311° C.) (314,359° C.)Comp.   0 wt. % 27.4 0.6  0.6  7.8 Ex. 3 μmol/g μmol/g μmol/g μmol/g     (109° C.)  (96° C.)    (241° C.) (287,349° C.)

TABLE 3 Performance Data for Example 1 Example Number: Example 1Catalyst descriptor: V—Ti—P, 2.5 wt. % Potassium Liquid feed molarcomposition 12/1/4.09 HOAc/Trioxane/Water Liquid feed flow rate (mL/min)0.089 Nitrogen flow rate (SCCM) 49 Air flow rate (SCCM) 21 Time betweensamples (h) 1.0 3.0 23 Total run time (h) 1.0 4.0 27 Product, g 4.8016.48 128.64 Reactants fed, g 5.71 17.11 131.41 GC/HPLC ResultsFormaldehyde, wt % 1.23 1.73 2.12 Acetone, wt % 0.04 0.05 0.04 MeOAc, wt% 0.14 0.13 0.13 Water, wt % 16.32 16.42 15.73 HOAc, wt % 60.45 65.367.59 Acrylic acid, wt % 17.23 18.5 17.35 HOPr, wt % Total knowns, wt %95.46 102.16 102.99 Calculated Data mmol HOAc fed 77.54 232.18 1783.32mmol HOAc in prod 48.32 179.21 1447.92 mmol HOAc consumed 29.22 52.97335.39 mmol H2CO fed 19.40 58.09 446.20 mmol H2CO in product 1.97 9.4990.81 mmol acrylic acid formed 11.48 42.31 309.73 mmol MeOAc formed 0.090.28 2.27 mmol acetone formed 0.04 0.13 0.97 mole ratio AA/acetone315.62 324.15 317.82 mmol HOAc unaccounted for 17.55 10.04 20.99 KeyMetrics % H2CO conversion 89.87 83.66 79.65 % selectivity to acrylicacid from 65.98 87.21 87.28 H2CO % yield acrylic acid from H2CO 59.2972.96 69.52 % HOAc accountability 77.36 95.68 98.82 mole acrylicacid/kg-hr 2.30 2.83 2.70

TABLE 4 Performance Data for Comparative Example 1 Example Number:Comparative Example 1 Catalyst descriptor: V—Ti—P, 0 wt. % PotassiumLiquid feed molar composition 12/1/4.09 HOAc/Trioxane/Water Liquid feedflow rate (mL/min) 0.089 Nitrogen flow rate (SCCM) 49 Air flow rate(SCCM) 21 Time between samples (h) 1.0 3.0 23 Total run time (h) 1.0 4.027 Product, g 5.34 16.7 130.42 Reactants fed, g 5.84 17.08 131.7 GC/HPLCResults Formaldehyde, wt % 4.18 4.47 4.72 Acetone, wt % 0.073 0.0960.096 MeOAc, wt % 0.184 0.195 0.206 Water, wt % 17.15 13.44 12.56 HOAc,wt % 66.14 70.01 69.44 Acrylic acid, wt % 12.84 13.68 13.57 HOPr, wt %0.016 0.005 0.005 Total knowns, wt % 100.58 101.9 100.6 Calculated Datammol HOAc fed 79.19 231.79 1787.04 mmol HOAc in prod 58.82 194.701508.14 mmol HOAc consumed 20.38 37.09 278.91 mmol H2CO fed 19.81 58.00447.13 mmol H2CO in product 7.43 24.86 204.99 mmol acrylic acid formed9.52 31.70 245.60 mmol MeOAc formed 0.13 0.44 3.63 mmol acetone formed0.07 0.28 2.16 mole ratio AA/acetone 141.77 114.85 113.93 mmol HOAcunaccounted for 10.60 4.39 25.37 Key Metrics % H2CO conversion 62.4957.14 54.15 % selectivity to acrylic acid from 76.85 95.67 101.43 H2CO %yield acrylic acid from H2CO 48.02 54.67 54.93 % HOAc accountability86.62 98.10 98.58 mole acrylic acid/kg-hr 1.86 2.12 2.13

TABLE 5 Performance Data for Comparative Example 2 Example Number:Comparative Example 2 Catalyst descriptor: V—Ti—P, 9.25 wt. % PotassiumLiquid feed molar composition 12/1/4.09 HOAc/Trioxane/Water Liquid feedflow rate (mL/min) 0.089 Nitrogen flow rate (SCCM) 49 Air flow rate(SCCM) 21 Time between samples (h) 1.0 3.0 23 Total run time (h) 1.0 4.027 Product, g 4.95 16.64 129.87 Reactants fed, g 5.71 17.14 131.41GC/HPLC Results Formaldehyde, wt % 8.38 7.97 8.57 Acetone, wt % MeOAc,wt % 0.23 0.22 0.20 Water, wt % 15.06 13.79 13.34 HOAc, wt % 73.97 73.9373.90 Acrylic acid, wt % 5.47 4.64 4.45 HOPr, wt % Total knowns, wt %103.11 100.55 100.46 Calculated Data mmol HOAc fed 77.54 232.61 1783.32mmol HOAc in prod 60.97 204.86 1598.23 mmol HOAc consumed 16.56 27.74185.08 mmol H2CO fed 19.40 58.20 446.20 mmol H2CO in product 13.81 44.16370.62 mmol acrylic acid formed 3.76 10.71 80.20 mmol MeOAc formed 0.150.49 3.51 mmol acetone formed 0.00 0.00 0.00 mole ratio AA/acetone n/an/a n/a mmol HOAc unaccounted for 12.65 16.54 101.38 Key Metrics % H2COconversion 28.80 24.12 16.94 % selectivity to acrylic acid from 67.2676.33 106.12 H2CO % yield acrylic acid from H2CO 19.37 18.41 17.97 %HOAc accountability 83.68 92.89 94.32 mole acrylic acid/kg-hr 0.75 0.710.70

TABLE 6 Performance Data for Comparative Example 3 Comparative Example 3Catalyst Descriptor V—Ti—P Liquid feed molar ratio 12/1/4.09(HOAc/Trioxane/H2O) Liquid feed flow rate (mL/min) 0.089 Nitrogen flowrate (SCCM) 49 Air flow rate (SCCM) 21 Time between samples (h) 1.0 3.023 Total reaction time (h) 1.0 4.0 27 Product, g 5.42 16.72 130.91Reactants fed, g 5.762 17.1 131.39 GC/HPLC Results Formaldehyde, wt %6.61 6.87 6.78 Acetone, wt % 0.068 0.063 0.065 MeOAc, wt % Water, wt %8.83 8.96 9.15 HOAc, wt % 72.59 73.16 72.15 Acrylic acid, wt % 8.68 8.358.98 HOPr, wt % Total knowns, wt % 96.85 97.4 97.12 Key Metrics % H2COconversion 39.03 34.13 33.75 % selectivity to acrylic acid from 85.4997.78 108.32 H2CO % yield acrylic acid from H2CO 33.37 33.37 36.56 %HOAc accountability 92.36 96.28 97.52 mole acrylic acid/kg-hr 1.29 1.291.42

The invention has been described in detail with particular reference topreferred embodiments thereof, but it will be understood that variationsand modifications can be effected within the spirit and scope of theinvention.

We claim:
 1. A catalyst composition comprising a mixed oxide of vanadium(V), titanium (Ti), phosphorus (P), and alkali metal (M), wherein thetitanium component is the residue of an organo-titanium compound,wherein the organo-titanium compound is titanium(IV) bis(ammoniumlactate)dihydroxide.
 2. The catalyst composition according to claim 1,which has the general formula VTi_(a)P_(b)M_(c)O_(d), wherein a is anumber from 0.3 to 6.0, b is a number from 2.0 to 13.0, c is a numberfrom 0.01 to 1.25, and d is the number of atoms required to satisfy thevalences of V, Ti, P, and M.
 3. The catalyst composition according toclaim 2, wherein a ranges from 1.0 to 4.0, b ranges from 4.0 to 10.0,and c ranges from 0.25 to 0.75.
 4. The catalyst composition according toclaim 1, wherein the alkali metal is selected from at least one oflithium, sodium, potassium, rubidium, and cesium.
 5. The catalystcomposition according to claim 1, wherein the alkali metal comprisespotassium.
 6. The catalyst composition according to claim 1, whichfurther comprises a pre-shaped support.
 7. The catalyst compositionaccording to claim 6, wherein the pre-shaped support comprises silica,alumina, titanium oxide, titanium pyrophosphate, zirconium oxide, orzirconium pyrophosphate.
 8. The catalyst composition according to claim6, wherein the pre-shaped support has a particle size ranging from 0.1mm to 20 mm.
 9. A method for preparing a catalyst composition comprisinga mixed oxide of vanadium (V), titanium (Ti), phosphorus (P), and alkalimetal (M); wherein the method comprises: (a) providing an aqueoussolution comprising an organo-titanium compound, wherein theorgano-titanium compound is titanium(IV) bis(ammoniumlactate)dihydroxide; (b) adding a vanadium compound, a phosphoruscompound, and an alkali metal compound to the aqueous titanium solutionto form a mixture of catalyst components; (c) heat-treating the mixture;(d) removing water from the heat-treated mixture to obtain a solidresidue comprising the catalyst components; and (e) calcining the solidresidue at an elevated temperature in the presence of air to obtain thecatalyst composition.
 10. The method according to claim 9, wherein thewater removing step (d) comprises distillation or evaporation.
 11. Themethod according to claim 9, wherein the water removing step (d)comprises adding an anti-solvent to the mixture to precipitate out thecatalyst components and separating the precipitate from the liquid toobtain the solid residue.
 12. The method according to claim 11, whereinthe precipitate is separated from the liquid by filtration.
 13. Themethod according to claim 11, wherein the anti-solvent is a polarcompound selected from alcohols, ketones, aldehydes, ethers, and esters.14. The method according to claim 13, wherein the anti-solvent is analcohol.
 15. The method according to claim 9, wherein the catalystcomposition has the general formula VTi_(a)P_(b)M_(c)O_(d), wherein a isa number from 0.3 to 6.0, b is a number from 2.0 to 13.0, c is a numberfrom 0.01 to 1.25, and d is the number of atoms required to satisfy thevalences of V, Ti, P, and M.
 16. The method according to claim 15,wherein a ranges from 1.0 to 4.0, b ranges from 4.0 to 10.0, and cranges from 0.25 to 0.75.
 17. The method according to claim 9, whereinthe alkali metal is selected from at least one of lithium, sodium,potassium, rubidium, and cesium.
 18. The method according to claim 9,wherein the alkali metal comprises potassium.
 19. The method accordingto claim 9, wherein the catalyst composition further comprises apre-shaped support.
 20. The method according to claim 19, wherein thepre-shaped support is added to the mixture of catalyst components beforethe heat-treating step (c).
 21. The method according to claim 9, whichfurther comprises adding a bifunctional compound to the mixture ofcatalyst components before the heat-treating step (c), wherein thebifunctional compound is selected from at least one of citric acid,lactic acid, glycolic acid, oxalic acid, ethylene glycol, butane diol,pentane diol, and hexane diol.
 22. The method according to claim 21,wherein the bifunctional compound comprises lactic acid.
 23. A processfor preparing a 2,3-unsaturated carboxylic acid, comprising: contactinga formaldehyde source with a carboxylic acid in the presence of acondensation catalyst under vapor-phase condensation conditions toobtain the 2,3-unsaturated carboxylic acid, wherein the condensationcatalyst comprises a mixed oxide of vanadium (V), titanium (Ti),phosphorus (P), and alkali metal (M), and wherein the titanium componentis derived from an organo-titanium compound, wherein the organo-titaniumcompound is titanium(IV) bis(ammonium lactate)dihydroxide.
 24. Theprocess according to claim 23, wherein the formaldehyde source isformaldehyde, 1,3,5-trioxane, dimethoxymethane, or diacetoxymethane andthe carboxylic acid is acetic acid or propionic acid.
 25. The processaccording to claim 23, wherein the formaldehyde source is an aqueoussolution of formaldehyde, 1,3,5-trioxane, dimethoxymethane, ordiacetoxymethane and the carboxylic acid is acetic acid or propionicacid.
 26. The process according to claim 25, wherein the aqueoussolution comprises from 30 to 65 weight percent of formaldehyde.
 27. Theprocess according to claim 23, wherein the alkali metal is selected fromat least one of lithium, sodium, potassium, rubidium, and cesium. 28.The process according to claim 23, wherein the alkali metal comprisespotassium.
 29. The process according to claim 23, wherein the catalystcomposition further comprises a pre-shaped support.